In this study, composites of poly (hydroxybutyrate-co-valerate) (PHBV) with untreated luffa fibers (ULF) and NaOH-H2O2 treated luffa fibers (TLF) were prepared by hot press forming. The properties of luffa fibers (LFs) and composites were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and other analysis methods. Results showed that pre-treatment effectively removed pectin, hemicellulose, and lignin, thus reducing the moisture absorptivity of LFs. The flexural strength of TLF/PHBV was higher than that of ULF/PHBV. With 60% LF content, the flexural strengths of ULF/PHBV and TLF/PHBV reached 75.23 MPa and 90.73 MPa, respectively, 219.7% and 285.6% more than that of pure PHBV. Water absorptivities of composites increased with increase in LF content. Water absorptivity of TLF/PHBV was lower than that of ULF/PHBV. The flexural strengths of composites decreased after immersion in water at room temperature. Meanwhile, flexural strength of TLF/PHBV was lower than that of ULF/PHBV. Pretreatment of LFs effectively improved the bonding between fibers and PHBV, resulting in enhanced and thus improved the moisture resistance of composites.